JP2008108719A - Manufacturing method of member for plasma display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method which easily manufactures a PDP member with high luminous efficiency and high performance. <P>SOLUTION: A photosensitive partition paste composed of an inorganic component containing low softening point glass powder and an organic component containing a photosensitive organic component is applied on a substrate and dried, to form a first partition paste layer. A photosensitive organic component and photosensitive electrode paste containing conductive particles with 1 to 200 nm of several times of a mean diameter are applied on the first partition paste layer and dried, to form an electrode paste layer. A laminate composed of the first partition paste layer and the electrode paste layer is exposed collectively and developed collectively, to form a laminate of a first partition pattern and an electrode pattern. The photosensitive partition paste is applied so as to cover the laminate of the first partition pattern and the electrode pattern and dried, to form a second partition paste layer. The second partition paste layer is exposed and developed, to form a laminate partition pattern composed of the first partition pattern, the electrode pattern, and a second partition pattern covering them. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a member for a plasma display.

  Plasma discharge is generated between the anode and cathode electrodes facing each other in a discharge space provided between a plasma display panel (hereinafter referred to as “PDP”), a front plate and a back plate, and is enclosed in the discharge space. The display is performed by irradiating the phosphor provided in the discharge space with ultraviolet rays having a very short wavelength such as 147 nm and 172 nm generated from a discharge gas such as a mixed gas of Xe-Ne. In addition, partition walls (also referred to as barriers or ribs) are provided in order to suppress the spread of the discharge to a certain area and perform display in a prescribed cell, and at the same time, ensure a uniform discharge space. As the shape of the partition wall, a stripe shape or a lattice shape having a width of about 20 to 120 μm and a height of 50 to 250 μm is generally used.

  An alternating current (AC) type PDP generally has a structure as shown in FIG. That is, the front plate 1 has a configuration in which a transparent electrode (scan electrode 3 and sustain electrode 4), a bus electrode 5, a transparent dielectric layer 6, and a MgO protective film 7 are formed on a glass substrate 2. The back plate 8 has a structure in which an address electrode 10, a dielectric layer 11, barrier ribs 12, and phosphors (a red phosphor 13, a green phosphor 14, and a blue phosphor 15) are formed on a glass substrate 9. In front plate 1, scan electrode 3 and bus electrode 5, and sustain electrode 4 and bus electrode 5 are laminated and electrically connected. By applying an alternating pulse voltage to the stacked body of the scan electrode 3 and the bus electrode 5 and the stacked body of the sustain electrode 4 and the bus electrode 5 positioned adjacent to the stacked body, discharge starts from the gap between the transparent electrodes. The surface light emission is performed while maintaining the surface discharge on the surface of the protective film. Light generated by exciting phosphors (red phosphor 13, green phosphor 14, and blue phosphor 15) formed on back plate 8 by ultraviolet rays generated by this discharge is used as display light.

  When the conventional PDP as described above has a high definition, there is a problem that the light emission efficiency (luminance with respect to the input power to a constant light emission area) is likely to decrease. This is because it is difficult to secure the discharge gap, the discharge area is reduced, and the like. First, the discharge space is reduced by reducing the size of the cells with higher definition, while the distance between the electrodes between adjacent cells is set to a certain value or more to prevent discharge interference with the adjacent cells. Since it cannot be made very large, it tends to be a discharge in a very small region, and since the discharge form is a surface discharge, a positive column with high generation efficiency of ultraviolet rays is not generated, and the discharge mode is restricted to a negative glow. . Therefore, since the ultraviolet ray generation efficiency is low, the light emission efficiency of display light from the phosphor tends to be low. In particular, in a high-definition PDP for high-vision applications and the like, the distance between the discharge site, the barrier ribs, and the phosphor is relatively short, and charged particles such as ions and electrons are easily diffused, thereby further narrowing the discharge region. The fact that the discharge form is a surface discharge is that the generated ultraviolet rays are also irradiated in the direction of the front plate 1 where no phosphor is formed, and most of them are not used for excitation of the phosphor and generation of display light. This also causes a decrease in luminous efficiency.

  Further, the front plate 1 is required to have a charge accumulation function at the time of selecting a display pixel and a display light transmission function. Therefore, the transparent dielectric layer 6 having a thickness of 20 to 50 μm is formed. The visible light transmittance of the transparent dielectric layer 6 is about 70 to 80%, a part of the display light is absorbed, and not all is used as a display, and a loss occurs. From the standpoint of display light transmission, the presence of transparent electrodes (scan electrodes 3 and sustain electrodes 4) made of ITO or the like present on the front plate 1 is also hindered.

  Furthermore, since the discharge region is limited to the vicinity of the transparent electrode, it has been difficult to efficiently generate ultraviolet rays. Further, the front plate 1 having the above-described configuration has many manufacturing processes, which causes a decrease in yield and an increase in cost.

  As described above, the major problems of the PDP are high luminous efficiency and low cost. In order to solve this problem, a counter discharge type PDP has been proposed (Patent Document 1). In the counter discharge type PDP described in Patent Document 1, a portion corresponding to a partition is formed into a lattice-like thick film ceramic sheet, and a back plate on which a writing electrode, a partition and a phosphor are formed, and a partition and a phosphor are formed. It has a three-layer structure in which a thick film ceramic sheet is sandwiched between front plates. A sustain electrode is formed in the thick film ceramic sheet, and a counter discharge is aimed at improving luminous efficiency. However, high-definition of the thick film ceramic sheet is difficult due to the process. In addition, since the electrode gap (= discharge gap) is long, the discharge start voltage becomes high, and a higher withstand voltage IC than before is required, which increases the cost of the drive circuit, the back plate, the thick film ceramic sheet, There is a problem that accuracy is required for alignment of the front plate, resulting in a decrease in yield and an increase in cost.

  On the other hand, a counter discharge type PDP having an electrode inside a partition wall of a back plate has been proposed (see Patent Document 2). The PDP described in Patent Document 2 uses an electrode formed inside the partition wall as a display electrode, for example, so that a gap between the electrodes can be made large and becomes closer to a discharge mode with a positive column. The efficiency can be increased, and as a result, the luminous efficiency of display light from the phosphor can be increased. Moreover, since it is a counter discharge between the electrodes which exist in the inside of the partition which provided the fluorescent substance on the surface, an ultraviolet-ray is efficiently utilized for excitation of a fluorescent substance. Furthermore, since there is no need to provide a dielectric layer or a transparent electrode on the front plate, there is little loss due to absorption in the front plate.

As a method for forming such a partition with a built-in electrode, Patent Document 2 describes a photolithography method using a known photosensitive electrode paste. However, in the method using a known photosensitive electrode paste, since the light transmittance of the electrode paste coating layer is small, the exposure of the lower layer of the partition wall, the electrode layer, and the upper layer of the partition wall is performed as described in Patent Document 2, respectively. There was a problem that the number of processes would increase because they had to be performed individually. Moreover, since the electrode layer cannot be thickened, there is a problem that the discharge area of the counter discharge is narrow.
JP 2004-235042 A (pages 5 to 8) JP 2004-241379 A (pages 10 to 11)

  The present invention focuses on the above-mentioned problems of the prior art and provides a method for easily producing a member for PDP having high luminous efficiency.

  In order to solve the above problems, the present invention has the following configuration. That is, according to the present invention, a first barrier rib paste layer is formed by applying and drying a photosensitive barrier rib paste comprising an inorganic component including a low softening point glass powder and an organic component including a photosensitive organic component on a substrate. A photosensitive electrode paste containing a photosensitive organic component and conductive particles having a number average particle diameter of 1 to 200 nm is applied onto the partition wall paste layer and dried to form an electrode paste layer. The first partition paste layer and the electrode A laminated body composed of paste layers is collectively exposed and collectively developed to form a first barrier rib pattern and electrode pattern laminated body, and a photosensitive barrier rib paste is applied so as to cover the first barrier rib pattern and electrode pattern laminated body; A product comprising the first barrier rib pattern, the electrode pattern, and the second barrier rib pattern covering the first barrier rib paste layer by drying to form a second barrier rib paste layer, exposing and developing the second barrier rib paste layer. A method for producing a display member characterized by forming a partition wall pattern and collectively firing the laminated partition wall pattern, or an inorganic component containing a low softening point glass powder and a photosensitive material An alkali-developable photosensitive barrier rib paste composed of an organic component containing a photosensitive organic component is applied and dried to form a first barrier rib paste layer. The photosensitive organic component and the number average particle size are on the first barrier rib paste layer. A water-developable electrode paste containing 1 to 200 nm conductive particles is applied and dried to form an electrode paste layer, and the laminate composed of the first partition paste layer and the electrode paste layer is collectively exposed to neutrality. The first barrier rib paste layer and the electrode pattern laminate are formed by development using a water-based developer, and photosensitive so as to cover the first barrier rib paste layer and electrode pattern laminate. A wall paste is applied and dried to form a second partition paste layer, which is exposed to light and developed using an alkaline developer, and includes the first partition pattern, the electrode pattern, and a second partition pattern covering them. A method for producing a member for a display, comprising: forming a barrier rib pattern and firing the laminate barrier rib pattern at once to form barrier ribs having electrodes therein.

  According to the present invention, it is possible to provide a method for easily producing a PDP member having high luminous efficiency.

  As a result of intensive studies on a method for producing a display member such as a PDP having high luminous efficiency at a low cost, the inventors have found that this can be achieved by the production method described below. That is, according to the present invention, a first barrier rib paste layer is formed by applying and drying a photosensitive barrier rib paste comprising an inorganic component including a low softening point glass powder and an organic component including a photosensitive organic component on a substrate. A photosensitive electrode paste containing a photosensitive organic component and conductive particles having a number average particle diameter of 1 to 200 nm is applied onto the partition wall paste layer and dried to form an electrode paste layer. The first partition paste layer and the electrode A laminated body composed of paste layers is collectively exposed and collectively developed to form a first barrier rib pattern and electrode pattern laminated body, and a photosensitive barrier rib paste is applied so as to cover the first barrier rib pattern and electrode pattern laminated body; A product comprising the first barrier rib pattern, the electrode pattern, and the second barrier rib pattern covering the first barrier rib paste layer by drying to form a second barrier rib paste layer, exposing and developing the second barrier rib paste layer. Forming a barrier rib pattern, it is important to form a partition wall having an electrode therein by co-firing the laminated barrier rib pattern. The details of the present invention will be described below with respect to a method for producing a structure having one electrode in a partition, but the present invention is also applicable to a structure including two or more electrode layers in a partition. The process can be simplified as the number increases.

  FIG. 1 is a flowchart schematically showing a method for producing a display member of the present invention.

Hereafter, the manufacturing method of the member for a display of this invention is demonstrated along the process of (a)-(h) shown in FIG.
First, in the step (a), a photosensitive partition paste is applied on the glass substrate 2 and dried to form a first partition paste layer 16. Here, the glass substrate 2 may be composed of a single glass substrate, or in the case of a PDP substrate having a configuration as shown in FIG. 2 described later, a conductive material such as silver on the glass substrate. The dielectric layer 11 mainly composed of the address electrode 10 and low dielectric glass may be formed of metal. When the address electrode and the dielectric layer described above are formed by baking using a paste composed of an organic component and an inorganic component, the address electrode 10 and the dielectric layer 11 that have been fired in advance may be formed. The precursor of the address electrode 10 and the precursor of the dielectric layer 11 before firing may be provided.

  The photosensitive paste (photosensitive barrier rib paste and photosensitive electrode paste) as used in the present invention is a photocrosslinking, photopolymerization by irradiating actinic rays to the coating film after coating and drying. , A paste whose chemical structure changes through a reaction such as photodepolymerization or photo-denaturation, and that can be developed with a developer.

  The photosensitive partition paste used in the present invention must have a low softening point glass, a photosensitive organic component selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer, a polymerization initiator, and an organic solvent. Ingredients. Furthermore, if necessary, additive components such as fillers, non-photosensitive polymer components, antioxidants, organic dyes, sensitizers, sensitizers, plasticizers, thickeners, dispersants, precipitation inhibitors, etc. It is composed by adding. The photosensitive barrier rib paste used in the present invention, particularly the photosensitive barrier rib paste used for forming the first barrier rib paste layer, is preferably an alkali developable photosensitive barrier rib paste layer. Here, the alkali developability means that it is dissolved in an alkaline aqueous developer having a pH of 9 to 14 but not dissolved in a neutral aqueous developer having a pH of 6 to 8 in the state before exposure, After exposure, it refers to those having the property of not dissolving in either an alkaline aqueous developer having a pH of 9 to 14 or a neutral aqueous developer having a pH of 6 to 8.

  In the present invention, the low softening point glass powder refers to a glass powder having a load softening temperature in the range of 400 to 600 ° C. This is because when the load softening temperature is within this range, there is no deformation of the pattern during sintering, and the meltability becomes appropriate. The filler is added to improve pattern strength and firing shrinkage, and refers to inorganic particles that hardly melt and flow even at the firing temperature. Specifically, it refers to an inorganic particle that does not have a softening temperature, a melting point, or a decomposition temperature at 600 ° C. or lower and exists as a solid at 600 ° C. By adding a filler, the shrinkage | contraction by baking of a pattern can be suppressed or the intensity | strength of a pattern can be improved. As the filler, high melting point glass having a load softening temperature of 600 to 1200 ° C., ceramic powder such as cordierite, alumina, silica, magnesia, zirconia, or the like is used.

  As the photosensitive polymer, an alkali-soluble polymer can be preferably used. This is because, since the photosensitive polymer has alkali solubility, an alkaline aqueous solution can be used as a developing solution instead of an organic solvent having an environmental problem. As the alkali-soluble polymer, an acrylic copolymer can be preferably used. An acrylic copolymer is a copolymer containing at least an acrylic monomer as a copolymerization component.

  Examples of the non-photosensitive polymer component include cellulose compounds such as methyl cellulose and ethyl cellulose, and high molecular weight polyethers. The photosensitive monomer is a compound containing a carbon-carbon unsaturated bond.

  After preparing the above various components so as to have a predetermined composition, the mixture can be homogeneously mixed and dispersed with a three roller or kneader to produce a photosensitive partition paste. As a coating method, methods such as screen printing, bar coater, roll coater, die coater, and blade coater can be used. The coating thickness can be adjusted by the number of coatings, the screen mesh, and the paste viscosity. Drying is performed using a hot air drier, IR drier, etc., and the drying temperature and time can be adjusted by the solvent and coating thickness of the paste used.

  Next, in step (b), a photosensitive electrode paste is applied on the first partition paste layer 16 described above, and the applied photosensitive electrode paste is dried to form an electrode paste layer 17.

  The photosensitive electrode paste used in the present invention contains, as essential components, a photosensitive organic component, a polymerization initiator, an organic solvent, and conductive particles selected from at least one of a photosensitive monomer, a photosensitive oligomer, and a photosensitive polymer. If necessary, binders, UV absorbers, sensitizers, sensitizers, polymerization inhibitors, plasticizers, thickeners, antioxidants, dispersants, organic or inorganic precipitation inhibitors and leveling agents, etc. Additive component, low softening point glass, and filler.

  As the conductive particles contained in the photosensitive electrode paste of the present invention, those having a number average particle diameter of 1 to 200 nm are used. In general, the conductive particles are opaque or have a large difference in refractive index from the organic component in the electrode paste layer 17, so that the particle size of the conductive particles in the electrode paste layer is larger than the wavelength of the actinic ray used for exposure. Then, the actinic ray is blocked, reflected, or scattered, so that the electrode paste layer 17 and the first barrier rib paste layer 16 cannot be patterned by batch exposure and batch development. In the present invention, the number average particle diameter of the conductive particles contained in the photosensitive electrode paste is set to 1 to 200 nm to prevent reflection and scattering, and the electrode paste layer 17 and the first barrier rib paste layer 16 are collectively formed. The laminated body of the first partition pattern 21 and the electrode pattern 22 can be formed with high accuracy by exposure and batch development. In addition, since the electrode paste layer 17 has good actinic ray transmission, high-accuracy patterning is possible even when the electrode paste layer 17 is thick, and as a result, according to the method for manufacturing a member for PDP of the present invention. The thickness of the electrode incorporated in the partition of the manufactured PDP member can be increased, and the discharge area of the counter discharge can be widened. The thickness of the electrode is preferably 10 to 50 μm.

  When the particle size of the conductive particles is less than 1 nm, the surface resistance of the particle layer is rapidly increased, and therefore, the conductivity is lowered when the electrode layer is formed, which is not preferable. In addition, when the particle size of the conductive particles is 200 nm or more, due to the difference in refractive index from the organic component, the exposure light (ultraviolet rays) is scattered, so that the transmittance is lowered, and batch exposure with the barrier rib paste layer is possible. It will disappear. The conductive particles are one or more selected from metals such as Au, Ag, Pd, Pt, Rh, Ru, Cu, Fe, Ni, Co, Sn, In, Al, Ta, Sb, Zn, and Ti. Either metal fine particles made of metal or oxide fine particles such as tin oxide, indium oxide, and antimony oxide can be used. When the conductive particles are made into a paste, the particles may be used as they are or may be used as a sol. The number average particle diameter of the conductive particles is determined by the dynamic light scattering particle size distribution meter, field emission scanning electron microscope (FE-SEM), transmission electron microscope (TEM) in the state where the conductive particles are in a powder or dispersed sol state. Etc. can be measured. When FE-SEM, TEM, or the like is used, the number average particle diameter can be determined by measuring 100 arbitrary conductive particles in a range of 1 μm × 1 μm.

  As the photosensitive organic component of the photosensitive electrode paste in the present invention, a compound having an ethylenically unsaturated group is preferably used. Examples of such polymerizable monomers include monomers having one or more photopolymerizable (meth) acrylate groups or aryl groups.

  As the binder polymer used for the photosensitive electrode paste, cellulose compounds such as methyl cellulose and ethyl cellulose, high molecular weight polyethers, acrylic resins and the like can be used. In the method for producing a display member of the present invention, by using a water-soluble binder polymer as described later, the photosensitive electrode paste is water developable, that is, soluble in a neutral aqueous developer before exposure. It is preferable to make it insoluble in a neutral aqueous developer after exposure. The neutral aqueous developer refers to water or an aqueous solution having a pH in the range of 6-8.

For example, as the water-soluble polymer, an acrylic copolymer having an ethylenically unsaturated group and a carboxyl group at the side chain or terminal is preferably used. Such a polymer has both photocuring properties and binder properties, and an ethylenically unsaturated group is added to an acrylic copolymer formed by copolymerizing an unsaturated carboxylic acid and an ethylenically unsaturated compound. It can manufacture by adding to. Preference is given to those having an ethylenically unsaturated group and a carboxyl group in the side chain.
Although it does not specifically limit as an ethylenically unsaturated compound polymerized as a monomer component of the acrylic copolymer which can be developed with water, Unsaturated carboxylic acid and the polyhydric alcohol and ethylenic represented by the following General formula (1) It is preferable to include a compound containing a monoester with an unsaturated carboxylic acid. In order to impart water developability to the coating film of the photosensitive glass paste, the binder polymer must have a certain level of water solubility. In order to give water solubility to the binder polymer, there is a method of introducing a hydrophilic site such as polyamide or polyether into the skeleton, but the coating film of the paste containing an inorganic component using these as a binder polymer swells, but is sufficient Since water solubility is not exhibited and a development residue remains, a good pattern cannot be obtained. Therefore, it is possible to impart sufficient water solubility to the binder polymer by introducing a water-soluble substituent such as a hydroxyl group or a carboxyl group into the side chain portion instead of the skeleton of the binder polymer.

  Also, if a paste containing a hydrophilic resin selected from polyether and polyester is used, the adhesion to the substrate will be high, and even in severe development environments such as spray development, pattern processing will be performed without peeling the exposed area. It has been known. Usually, in an extreme development environment in which a photosensitive coating film for water development is exposed and then spray development is performed using an alkaline developer, the exposed area is peeled off. If a photosensitive acrylic resin having a hydroxyl group is used, high development resistance can be obtained without adding an anti-peeling compound as a separate component, and exposure area peeling can be prevented even in a development environment using an alkaline developer. Is possible.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,3-propanediol, glycerin, polyglycerin, 1,3-butanediol, 1,4-butanediol, , 2-propanediol, neopentyl glycol, pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, trimethylolethane, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, Examples include 2,4-pentanediol, 1,2,6-hexanetriol, cyclohexanedimethanol and the like. Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof. Therefore, an ester of a polyhydric alcohol and an ethylenically unsaturated carboxylic acid represents an esterified product formed by a combination of the above polyhydric alcohol compound and an ethylenically unsaturated carboxylic acid.

  In the present invention, an unsaturated acid such as an unsaturated carboxylic acid is added as a component of the copolymer in order to introduce a carboxyl group into the side chain or terminal of the acrylic copolymer. Specific examples of the carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof.

  Examples of other copolymerizable components that can be polymerized with the copolymerized component include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n- Pentyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, allyl acrylate, butoxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl acrylate, isobonyl Acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate Relate, stearyl acrylate, phenoxyethyl acrylate, 2-methoxyethyl acrylate, octafluoropentyl acrylate, trifluoroethyl acrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate , Thiophenol acrylate, benzyl mercaptan acrylate, a monomer in which 1 to 5 of the aromatic ring hydrogen atoms are substituted with chlorine or bromine, or styrene, p-methylstyrene, o-methylstyrene, m- Methyl styrene, chlorinated styrene, brominated styrene, α-methyl styrene, chlorinated α-methyl styrene, brominated α-methyl styrene, chloromethyl Styrene, hydroxy styrene, carboxymethyl styrene, vinyl naphthalene, vinyl anthracene, vinyl carbazole, and those that were changed to methacrylate acrylate of the above compounds. In this invention, these can be used 1 type or in combination of 2 or more types.

  As a method for introducing an ethylenically unsaturated bond into a side chain, an ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. There is a method in which a carboxylic acid such as chloride, allyl chloride or maleic acid is reacted.

Examples of the ethylenically unsaturated compound having a glycidyl group include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, crotonic acid glycidyl ether, and isocrotonic acid glycidyl ether. In particular, glycidyl (meth) acrylate is preferably used.
Examples of the ethylenically unsaturated compound having an isocyanate group include (meth) acryloyl isocyanate and (meth) acryloylethyl isocyanate. In addition, the ethylenically unsaturated compound having a glycidyl group or an isocyanate group, acrylic acid chloride, methacrylic acid chloride or allyl chloride is 0.05 to 1 molar equivalent with respect to a mercapto group, amino group, hydroxyl group or carboxyl group in the polymer. It is preferable to make it react, More preferably, it is 0.1-0.8 molar equivalent. If the addition amount is less than 0.05 molar equivalent, the photosensitivity will be poor and pattern formation will be difficult, and if it is greater than 1 molar equivalent, the solubility of the unexposed area will decrease, which is not preferred.

  The acid value of the acrylic copolymer having an ethylenically unsaturated group and a carboxyl group at the side chain or terminal obtained by polymerizing the above components is preferably 2 to 50 mgKOH / g. More preferably, it is 5-40 mg / KOH. When the acid value exceeds 50 mgKOH / g, in the presence of glass powder containing zinc or lead, the ion crosslinking density due to the carboxyl group increases, the gelation of the paste is promoted, and the solubility of the unexposed part in the developer is increased. Causes a drop and paste pot life. On the other hand, when the acid value is 2 mgKOH / g or less, the content of the carboxyl group that affects the solubility of the unexposed area is too low, so the solubility of the unexposed area in the developing solution is remarkably lowered, and a high-definition pattern is obtained. It becomes difficult to be.

  The weight average molecular weight of the acrylic copolymer having an ethylenically unsaturated group and a carboxyl group at the side chain or terminal is preferably 5000 to 20000, more preferably 8000 to 15000. When the molecular weight is less than 5,000, the photosensitive copolymer has a weak action as a binder and the development resistance is lowered, and therefore, the exposed portion is peeled off. On the other hand, if the molecular weight is larger than 20000, the development resistance is too high, so that the solubility of the unexposed area is lowered and pattern formation becomes difficult.

  The polymerization initiator is selected from those that generate radical species.

  By adding an ultraviolet absorber to the photosensitive electrode paste, the scattered light inside the paste due to the exposure light can be absorbed and the scattered light can be weakened. As the ultraviolet absorber, benzophenone compounds, cyanoacrylate compounds, salicylic acid compounds, benzotriazole compounds, and indole compounds are used. In addition, when conductive particles in which zinc or titanium oxide or the like exhibits ultraviolet absorption characteristics are used as the conductive particles, the absorption characteristics of the paste layer can be controlled by the absorption wavelength and addition amount of the ultraviolet absorbent.

  As the low softening point glass used for the photosensitive electrode paste, it is preferable to use a glass having a refractive index, a softening temperature, a thermal expansion coefficient, and the like close to those of the low softening point glass used for the partition wall paste. When the same low softening point glass as the barrier rib paste is used, it is possible to match the refractive index with the barrier rib paste layer laminated on or under the electrode paste layer, so that light scattering during exposure can be suppressed, and further, the electrode pattern This is more preferable because firing shrinkage matches with the barrier rib pattern laminated on the top or bottom.

  After preparing these various components of the photosensitive electrode paste to have a predetermined composition, the photosensitive electrode paste can be prepared by uniformly mixing and dispersing with three rollers or a kneader. As a coating method, methods such as screen printing, bar coater, roll coater, die coater, and blade coater can be used. The coating thickness can be adjusted by the number of coatings, the screen mesh, and the paste viscosity. Drying is performed using a hot air drier, IR drier, etc., and the drying temperature and time can be adjusted by the solvent and coating thickness of the paste used.

  Next, in step (c), the laminated body composed of the first barrier rib paste layer 16 and the electrode paste layer 17 is collectively exposed using the electrode exposure photomask 20 at the optimum exposure amount, and the first barrier rib paste layer exposure portion. 18 and the electrode paste layer exposure part 19 were formed. In the present invention, since an electrode paste containing conductive particles having a volume average particle diameter of 1 to 200 nm smaller than the ultraviolet wavelength is used, the electrode paste layer has a high ultraviolet transmittance and is a laminate of the electrode paste layer and the partition paste layer. Can be batch exposed. The exposure may be performed by a mask exposure method using a photomask, as is performed by a general photolithography method. As the photomask to be used, either a negative type or a positive type is selected depending on the type of the photosensitive organic component. Alternatively, a method of directly drawing with a red or blue laser beam or the like without using a photomask may be used. As the exposure apparatus, a stepper exposure machine, a proximity exposure machine or the like can be used. In the case of performing a large area exposure, a small exposure area is obtained by performing exposure while relatively moving the electrode exposure photomask 20 and the substrate after applying a photosensitive paste on a substrate such as a glass substrate. It is possible to expose a large area with this exposure machine. The optimum exposure amount here means an exposure amount when the pattern shape becomes a rectangle or a trapezoid without peeling or meandering after development. The rectangle means the same width at the top and the bottom, and the trapezoid means that the width at the bottom is larger than the width at the top.

  Next, in the step (d), the laminate composed of the first partition paste layer 16 and the electrode paste layer 17 including the first partition paste layer exposure part 18 and the electrode paste layer exposure part 19 is collectively developed to obtain the first partition pattern 21. And the laminated body which consists of electrode pattern 22 is formed. In the step (d), when only the electrode paste layer 17 is developed to form a laminate composed of the first barrier rib paste layer 16 including the first barrier rib paste layer exposure part 18 and the electrode pattern 22, grooves between patterns are formed. Since the depth becomes shallower, it is preferable because application failure in the next step (e) can be suppressed. Development is usually performed by dipping, spraying, brushing, or the like. As the developer, an organic solvent, an alkaline aqueous solution, or a neutral aqueous developer that can dissolve the organic components in the photosensitive paste can be used. As the alkaline aqueous solution, sodium hydroxide, sodium carbonate, potassium hydroxide aqueous solution, aminoethanol aqueous solution or the like can be used. When only the electrode paste layer 17 is developed, for example, the first partition paste layer is made of an alkali-developable partition paste and the electrode paste layer is made of a water-developable electrode paste so that the first partition paste layer becomes insoluble. And batch development using a neutral aqueous developer. After the development, it is preferable to cure the laminated body of the first partition pattern 21 and the electrode pattern 22 by heat. By curing, disconnection and cracking when the electrode layer and the partition wall layer are simultaneously fired can be suppressed. The curing condition is usually about 150 to 250 ° C. and about 3 to 60 minutes. The term “cure” as used herein means a heat treatment that promotes the evaporation of the developer and the curing of the organic component due to the crosslinked structure of the organic component. For the curing, a hot air dryer or an IR dryer can be used.

  Next, in step (e), the laminated body composed of the first barrier rib pattern 21 and the electrode pattern 22 or the laminated body composed of the first barrier rib paste layer 16 including the first barrier rib paste layer exposure part 18 and the electrode pattern 22 is covered. The second barrier rib paste layer 23 is formed by applying and drying the photosensitive barrier rib paste. As the photosensitive barrier rib paste, a known photosensitive glass paste may be used similarly to the one used in the first barrier rib paste layer 16. In consideration of shrinkage during firing, it is more preferable to use a material containing a urethane compound capable of reducing shrinkage stress. Examples of the urethane compound include compounds represented by the following general formula (1).

_{^{R 1 - (R 4 -R 3}} ) n -R 4 -R 2 (1)
(R ¹ and R ² are selected from the group consisting of a substituent containing an ethylenically unsaturated group, hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and a hydroxyaralkyl group, and the same. R ³ is an alkylene oxide group or alkylene oxide oligomer, R ⁴ is an organic group containing a urethane bond, n is an integer of 1 to 10) such a urethane compound is ethylene oxide Preferably it contains units. More preferably, in the general formula (1), R ⁴ is an oligomer containing an ethylene oxide unit (hereinafter referred to as EO) and a propylene oxide unit (hereinafter referred to as PO), and the EO content in the oligomer Is within the range of 8 to 70% by mass. When the EO content is 70% by mass or less, the flexibility is further improved and the firing stress can be reduced, so that defects can be effectively suppressed. Furthermore, the thermal decomposability is improved, and the firing residue is less likely to occur in the firing step after the partition wall is formed. Moreover, compatibility with other organic components improves because EO content is 8% or more. It is also preferred that the urethane compound has a carbon-carbon double bond. When the carbon-carbon double bond of the urethane compound reacts with the carbon-carbon double bond of another crosslinking agent and is contained in the crosslinked product, polymerization shrinkage can be further suppressed.

  As a coating method, a method such as screen printing, a bar coater, a roll coater, a die coater, and a blade coater can be used in the same manner as the coating of the first partition paste layer 16. The coating thickness can be adjusted by the number of coatings, the screen mesh, and the paste viscosity. Drying is performed using a hot air drier, IR drier, etc., and the drying temperature and time can be adjusted by the solvent and coating thickness of the paste used.

  Next, in the step (f), the obtained laminate is collectively exposed with an optimum exposure amount using the photomask 24 for partition exposure. The exposure is generally performed by mask exposure using a photomask, as in the case of exposure of the laminate composed of the first partition paste layer 16 and the electrode paste layer 17 as described above, as in the normal photolithography method. . Here, as shown in FIG. 2 to be described later, when the electrode is not provided and exposed in the partition wall, the exposure portion exposed by the partition wall exposure photomask 24 is exposed using the above-described electrode exposure photomask 20 and developed. Thus, it is necessary to align the pattern obtained in such a manner as to be included in the pattern.

  Next, in step (g), the second barrier rib paste layer is developed to form a laminated barrier rib pattern 26 comprising the first barrier rib pattern, the electrode pattern, and the second barrier rib pattern covering them. The development can be performed by the same method as the development of the laminate composed of the first partition paste layer and the electrode paste layer.

  Next, in the step (h), the laminated barrier rib pattern 26 is collectively fired in a baking furnace to form barrier ribs 27 having electrodes therein. The firing atmosphere and temperature vary depending on the type of paste and substrate, but firing is performed in an atmosphere of air, nitrogen, hydrogen, or the like. As the firing furnace, a batch-type firing furnace or a belt-type continuous firing furnace can be used.

  As described above, according to the method for manufacturing a PDP member of the present invention, a partition having an electrode inside can be formed with high accuracy by a simple process including two exposure steps. Further, since the patterning with high accuracy is possible even when the thickness of the electrode paste layer 17 is large, the thickness of the electrode can be increased and the discharge area of the counter discharge can be widened.

  The member for PDP produced using the present invention can be used for both the back plate and the front plate of the PDP. As an example, a preferable configuration in the case where a PDP member produced using the present invention is used as a back plate and an electrode in a partition wall is used as a display (sustain) electrode will be described below. However, the present invention is not limited to this.

  FIG. 2 shows a first structure example of a PDP member manufactured by the manufacturing method of the present invention. In FIG. 2, in order to show the internal structure of the partition wall, the partition wall is partially cut away (shaded portion).

  In the first structural example shown in FIG. 2, the back plate 8 is provided with a stripe-shaped address electrode 10 on a glass substrate 9, and a dielectric layer 11 is provided so as to cover the address electrode.

  Further, a partition wall 12 including a main partition wall 30 substantially parallel to the address electrode 10 and an auxiliary partition wall 31 substantially orthogonal to the address electrode 10 is provided on the dielectric layer 11. It has a structure in which striped main electrodes 32 that are substantially orthogonal to each other are provided.

  The PDP of the present invention is not a general surface discharge type but a counter discharge type. Therefore, the gap between the electrodes can be increased as compared with the surface discharge type, and the discharge path can be made longer. That is, the generation probability of the positive column is increased, and the ultraviolet ray generation efficiency and the light emission efficiency can be increased. In addition, most of the counter discharge type PDPs so far are counter discharges between the front plate and the back plate, and in order to increase the discharge path length (= interelectrode gap), it is necessary to form higher barrier ribs, The aspect ratio is large, and it is not realistic from the viewpoint of processing accuracy and yield. In addition, when addressing is performed by opposing discharge between the front plate and the back plate, there is a problem that the gap between the electrodes becomes too long, the address voltage becomes high, a high voltage IC is required, and the cost increases. For this reason, the gap between electrodes in the counter discharge type was about 100 to 150 μm.

  The interelectrode gap in the structure of the present invention can be set to the same level as the interval between the discharge cells. For example, it is about 0.5 mm in the 42-inch VGA (640 × 480 pixels) class and about 0.3 mm in the XGA (1024 × 768 pixels) class. Therefore, the inter-electrode gap can be increased by 2 to 3 times or more as compared with the conventional counter discharge type without increasing the partition wall. In addition, the interelectrode gap is about 3 to 5 times that of the conventional surface discharge type. That is, it becomes closer to the discharge mode accompanied by the generation of the positive column, and the ultraviolet ray generation efficiency can be increased, that is, the light emission efficiency can be increased. Further, since the counter discharge is performed, the loss of ultraviolet rays to the front plate and the loss of charged particles to the barrier ribs are reduced, so that the luminous efficiency is increased from this viewpoint.

  In the conventional discharge type between the front plate and the back plate, the interelectrode gap, the partition wall height, and the discharge space volume could not be changed independently. However, in the structure of the present invention, the interelectrode gap is kept constant. Since the discharge space can be widened by increasing the height of the partition wall, the degree of freedom in cell design for increasing the ultraviolet ray generation efficiency and reducing the diffusion loss of charged particles can be increased without changing the discharge start voltage.

  Further, since it is not necessary to form electrodes on the front plate, the transparent dielectric layer and the transparent electrode layer are unnecessary, and the phosphor emission that has been lost by 20 to 30% can be effectively used as display light. Furthermore, since these need not be formed, the front plate production process can be greatly reduced. Further, since no bus electrode is required on the front plate, the aperture ratio of one pixel can be increased. Further, until now, most of the light emitted from the phosphor irradiated to the bus electrode has been absorbed and the display has not been used. However, since this can be used effectively, the luminance can be increased.

  In the PDP of the present invention, the display electrodes in the partition walls are preferably thick in the height (thickness) direction. As the display electrode is thicker, charges due to glow discharge are more easily stored on the side surfaces of the partition walls in the discharge cell, and the discharge space at the time of discharge is widened to improve the efficiency of generating ultraviolet rays. In the production method using the conventional photolithography method, the exposure light (ultraviolet ray) of the electrode layer is low. Therefore, the electrode layer may be formed unless the film thickness is about 1 μm to 5 μm by one application, exposure, and development. In order to increase the film thickness, coating and exposure had to be repeated several times. However, in the present invention, an electrode layer of about 1 μm to 50 μm can be formed by one application, exposure and development, respectively.

  Further, when the display electrode layer is a thick film of about 10 μm to 50 μm, for example, the cross-sectional shape of the display (sustain) electrode layer is preferably close to a rectangle. If the cross-sectional shape of the display (sustain) electrode layer is trapezoidal or inverted trapezoidal, the film thickness on the side surfaces of the partition walls, which are dielectric layers, varies, which is not preferable because the discharge may become unstable. Here, the inverted trapezoid means that the top width is larger than the bottom width. In the present invention, since the display (sustain) electrode can be formed in a rectangular shape, stable discharge occurs even when the film thickness is increased.

  FIG. 3 shows a second structural example of the PDP member manufactured by the manufacturing method of the present invention. In FIG. 3, in order to show the internal structure of the partition wall, the partition wall is partially notched (shaded portion).

As shown in FIG. 3, in the PDP member of the present invention, it is preferable that the electrode has a striped main electrode and an auxiliary electrode protruding from the main electrode in a direction facing each other. Thereby, the discharge start voltage can be lowered and stable discharge can be performed. The discharge start voltage is determined by Paschen's law (V _f = f (p · d), V _f : discharge start voltage, p: discharge gas pressure, d: distance between electrodes). V _f indicates a minimum with respect to the product of p · d. When the electrodes are arranged on the surface and / or inside of the barrier ribs, the distance between the electrodes becomes longer and the discharge start voltage becomes higher than that in the surface discharge as described above. However, as shown in FIG. By providing the auxiliary electrode protruding in the facing direction, the discharge start voltage can be lowered. This is because by providing the auxiliary electrode, the distance can be partially reduced by the distance between the display electrodes, so that a discharge easily occurs in the gap between the auxiliary electrodes (discharge gap). Connected.

  In view of the effect of reducing the discharge start voltage and the stability of the discharge, the gap between the auxiliary electrodes is preferably 50 to 800 μm. More preferably, it is 60-300 micrometers. Even more preferably, it is 70 to 150 μm. When the gap between the auxiliary electrodes is smaller than 50 μm, dielectric breakdown is likely to occur at the gap between the electrodes. Moreover, when larger than 800 micrometers, it becomes difficult to obtain the reduction effect of a discharge start voltage.

  The gap between the main electrodes is preferably 100 to 1000 μm although it depends on the size of the discharge cell to be produced. More preferably, it is 150-650 micrometers. If it is smaller than 100 μm, the discharge space becomes too narrow and stable discharge cannot be performed. This is because the discharge starting voltage is too large for practical use when it is larger than 1000 μm.

Further, although FIG. 3 shows an auxiliary electrode having a simple slit structure, one side may be tapered. That is, by providing a taper on the side of the adjacent discharge cell, erroneous discharge of the adjacent non-discharge cell (non-display cell) can be suppressed. In addition, a parallel slit shape is preferable from the viewpoint of uniformity in processing accuracy of the inter-electrode spacing.
In the case of AC type PDP, it is necessary to cover the electrode with an insulating material. However, when an auxiliary electrode is provided, the auxiliary electrode is embedded in the partition wall or formed on the surface of the partition wall in the same manner as the main electrode. Then, it is preferable to coat with an insulating material later. When the auxiliary electrode and the main electrode are arranged on the surface and / or inside of the partition wall, the partition wall shape is preferably a lattice shape or a waffle shape, not a stripe shape. A lattice-like partition wall is more preferable. This is because the auxiliary electrode may be formed inside the partition wall (main partition wall) that partitions the pixels in the horizontal direction and the main electrode may be formed inside the partition wall (auxiliary partition wall) for partitioning the pixels in the vertical direction.

  A case where a PDP is manufactured using the PDP member of the present invention, for example, as a back plate will be described below. However, the present invention is not limited to this.

  As the back plate and the front plate substrate of the present invention, “PD200” manufactured by Asahi Glass Co., Ltd. and “PP8” manufactured by Nippon Electric Glass Co., Ltd., which are heat resistant glass for PDP, can be used in addition to soda glass.

  In the back plate, first, address electrodes are formed in stripes at a pitch of discharge cells on a glass substrate with a metal such as silver, aluminum, chromium or nickel. As a method of forming, after applying a metal paste mainly composed of these metal powder and organic binder by screen printing, or after applying a photosensitive metal paste using a photosensitive organic component as an organic binder, It is possible to use a photosensitive paste method in which pattern exposure is performed using a photomask, unnecessary portions are dissolved and removed in a development step, and further, heated and baked at 400 to 600 ° C. to form an electrode pattern. Also, after depositing a metal such as chrome or aluminum on a glass substrate, apply a resist, pattern exposure and development using a photomask, and then use an etching method to remove unnecessary portions of the metal by etching. Can do. Furthermore, a dielectric layer may be provided on the address electrode layer in order to stabilize discharge.

  The partition wall of the present invention is formed on the glass substrate on which the address electrode is formed. The shape of the partition wall is not particularly limited. However, when the auxiliary electrode is used as shown in FIG. After the partition walls are formed, a partition wall for securing a clearance from the front side substrate may be further provided in order to improve the efficiency of evacuation after panel formation. The partition for the purpose of securing the clearance may also be formed together with the first partition pattern, the electrode pattern, and the second partition pattern covering them.

A phosphor is formed using a phosphor paste on a glass substrate on which address electrodes, barrier ribs, and display electrode pairs are formed. It can be formed by a photolithography method, a dispenser method, a screen printing method or the like using a photosensitive phosphor paste. The thickness of the phosphor is not particularly limited, but is 10 to 30 μm, more preferably 15 to 25 μm. The phosphor powder is not particularly limited, but the following phosphors are preferable from the viewpoint of light emission intensity, chromaticity, color balance, lifetime, and the like. Blue is an aluminate phosphor activated with divalent europium (for example, BaMgAl ₁₀ O ₁₇ : Eu) or CaMgSi ₂ O ₆ . In the case of green, Zn ₂ SiO ₄ : Mn, YBO ₃ : Tb, BaMg ₂ Al ₁₄ O ₂₄ : Eu, Mn, BaAl 1 ₂ O ₁₉ : Mn, BaMgAl ₁₄ O ₂₃ : Mn are preferable from the viewpoint of panel luminance. More preferably Zn ₂ SiO _4: is Mn. In red, (Y, Gd) BO ₃ : Eu, Y ₂ O ₃ : Eu, YPVO: Eu, and YVO ₄ : Eu are also preferable. More preferred is (Y, Gd) BO ₃ : Eu.

  After forming the phosphor, a part or all of the phosphor may be covered with an insulating material. The coating method and the like are the same as those described above for the partition wall coating, but the firing temperature of the layer covering the phosphor should be 550 ° C. or less in order to minimize phosphor degradation. Is preferred. More preferably, it is 510 degrees C or less.

  Next, although the front plate of the present invention is ultimately possible only with a glass substrate, a protective film (for example, MgO film) is formed on the glass substrate for the purpose of improving the sputter resistance of the glass substrate surface. Alternatively, a black stripe or a black matrix may be formed for the purpose of improving the bright room contrast. In addition, an address electrode can be formed on the front side for the purpose of improving the address voltage and margin of the display cell.

  After sealing the back plate and the front plate, the space formed between the two substrates is evacuated while heating, and then sealed with a discharge gas composed of helium, neon, xenon, or the like. Stop. Xe5-10% -Ne bal. Mixed gas is preferable in terms of both discharge voltage and luminance. In order to increase the generation efficiency of ultraviolet rays, Xe may be further increased to about 30%.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to this.
(Method for producing barrier rib paste)
Glass powder 60% by weight, binder (copolymer of methyl methacrylate and methacrylic acid (average molecular weight 25000, acid value 102) 10% by weight, photosensitive monomer (tetrapropylene glycol diacrylate) 10% by weight, photopolymerization initiator ( “Irgacure” 369), 17% by weight of γ-butyrolactone, glass powder, glass transition point 495 ° C., softening point 530 ° C., coefficient of thermal expansion 75 × 10 ⁻⁷ / ° C., density 2.54 g / cm ³ Each component of the organic component was mixed and dissolved, then added with the inorganic component, and kneaded with three rollers to prepare a paste composed of glass fine particles and the organic component. Defoamed with a machine.
(Measurement of number average particle diameter of conductive particles)
The number average particle size of the conductive particles was measured using a dynamic light scattering particle size distribution meter (Zeta Sizer; manufactured by Sysmex Corporation) before adding the paste.
(Production method of electrode paste)
Each component of the organic component was dissolved while being heated to 50 ° C., and then conductive particles and glass fine particles were added and kneaded using a kneader. As the conductive particles, silver paste (Finesphere SVND102; manufactured by Nippon Paint Co., Ltd.) is used for the electrode paste 1, indium tin oxide particles (Nanotech; manufactured by CI Chemical Co., Ltd.) are used for the electrode paste 2, and antimony is used for the electrode paste 3. Tin oxide (TWU-1; manufactured by Gemco Co., Ltd.) and silver particles (SPN10J; manufactured by Mitsui Metals) were used for the electrode paste 4. The composition of the prepared electrode paste is shown in Table 1. The details of the inorganic and organic components in Table 1 are as follows.

VY-10: Glass transition point 460 ° C., softening point 495 ° C.
Polymer 1: A product obtained by adding 0.4 equivalent of glycidyl methacrylate to a carboxyl group of a styrene / methyl methacrylate / methacrylic acid copolymer. Weight average molecular weight 43000, acid value 95
Polymer 2: A photosensitive acrylic polymer obtained by addition reaction of 0.9 molar equivalent of glycidyl methacrylate to a carboxyl group of a copolymer composed of 30% acrylic acid, 40% methyl methacrylate, and 30% glycerin monoacrylate. Acid value 10 mgKOH / g, weight average molecular weight 9000.
PDP400: Propylene glycol dimethacrylate TPA330: Trimethylolpropane triacrylate IC369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1
S20000: Solsparse 20000
γ-BL: gamma butyrolactone (preparation of base substrate)
The electrode paste 4 was applied and dried by screen printing on a 5-inch square glass substrate (PD-200; manufactured by Asahi Glass Co., Ltd.), and a dried coating film having a thickness of 10 μm was obtained. The coating film was exposed at an exposure amount of 400 mJ / cm ² using a 5-inch emulsion mask having a stripe pattern with a pitch of 300 μm and a width of 80 μm, and subjected to shower development with a 0.1 wt% 2-aminoethanol solution for 20 seconds. A pattern was formed. Next, a dielectric paste was applied on the electrode pattern by screen printing and dried, and after drying, a dielectric layer having a thickness of 6 μm was formed, which was used as a base substrate.
(Pattern processability evaluation)
When a laminated pattern composed of a partition wall layer and an electrode layer was formed on a 5-inch square glass substrate in a 40 cm ² (8 cm × 5 cm) region, the pattern in that region was not peeled off during processing, and there were no cracks during firing. The thing was pattern-processed (circle), and even if even one piece peeled and there was a crack, it was set as x.
(Measurement of relative luminous efficiency)
Luminous efficiency was determined as follows. First, the luminance B (cd / m ² ) of the produced PDP was measured using a colorimeter (CS-1000; manufactured by Minolta). The electric power W (W) applied to the PDP at this time was determined using a digital power meter (2532, manufactured by Yokogawa Electric Corporation). And luminous efficiency (eta) was calculated | required from following Formula.
η = πB · S / W
Here, S is the area (m ² ) of the display part of the manufactured PDP.
The light emission efficiency when the light emission efficiency of Comparative Example 4 was 100 was defined as the relative light emission efficiency.
(Example 1)
The partition paste was applied on the base substrate using a slit die coater so that the thickness of the first partition paste layer after drying was 120 μm, and dried at 100 ° C. for 60 minutes using a hot air dryer. The electrode paste 1 was applied thereon using a slit die coater so that the thickness of the electrode paste layer after drying was 40 μm, and dried at 100 ° C. for 30 minutes using a hot air dryer. Next, the laminate was subjected to alignment exposure at an exposure amount of 100 mJ / cm ² using a 5-inch emulsion mask having a repeated pattern of dimensions shown in FIG. 4, and shower development was performed for 3 minutes with a 0.2 wt% 2-aminoethanol solution. Then, a laminated pattern was formed. Next, using a slit die coater, the barrier rib paste is applied so as to cover the laminated pattern so that the thickness of the second barrier rib paste layer after drying is 180 μm, and dried at 100 ° C. for 90 minutes using a hot air dryer. Went. The laminate was subjected to alignment exposure at an exposure amount of 100 mJ / cm ² using a 5-inch emulsion mask having a repeated pattern of dimensions shown in FIG. 5, and shower-developed with a 0.2 wt% 2-aminoethanol solution for 4 minutes, A laminated pattern was formed. The laminated pattern was baked at 590 ° C., and a partition wall in which an electrode layer having a thickness of 20 μm was formed in the partition wall could be formed.
(Example 2)
A partition wall in which an electrode layer having a thickness of 20 μm was formed in the partition wall could be formed in the same manner as in Example 1 except that the electrode paste 2 was used instead of the electrode paste 1.
(Example 3)
A partition wall in which an electrode layer having a thickness of 20 μm was formed in the partition wall could be formed in the same manner as in Example 1 except that the electrode paste 3 was used instead of the electrode paste 1.
(Comparative Example 1)
The partition paste was applied on the base substrate using a slit die coater so that the thickness of the first partition paste layer after drying was 120 μm, and dried at 100 ° C. for 60 minutes using a hot air dryer. Next, the partition wall layer was subjected to alignment exposure at an exposure amount of 30 mJ / cm ² using a 5-inch emulsion mask having a repeated pattern of dimensions shown in FIG. 5, and then the electrode paste 4 was dried using a screen printer. The subsequent electrode paste layer was applied so as to have a thickness of 10 μm, and dried at 120 ° C. for 10 minutes using a hot air dryer. Next, the electrode layer was subjected to alignment exposure at an exposure amount of 300 mJ / cm ² using a 5-inch emulsion mask having a repetitive pattern of dimensions shown in FIG. 4, and shower-developed with a 0.1 w% 2-aminoethanol solution for 20 seconds. The electrode pattern was formed on the partition layer. Next, the barrier rib paste is applied on the laminate of the barrier rib layer and the electrode pattern using a slit die coater so that the thickness of the second barrier rib paste layer after drying is 50 μm, and is heated at 100 ° C. using a hot air dryer. Drying was performed for 30 minutes. The partition wall layer was subjected to alignment exposure at an exposure amount of 50 mJ / cm ² using a 5-inch emulsion mask having a repeated pattern of dimensions shown in FIG. 5 and shower-developed with a 0.1 wt% 2-aminoethanol solution for 4 minutes. A laminated pattern could be formed. The laminate pattern was baked at 590 ° C., and a partition wall in which an electrode layer having a thickness of 3 μm was formed in the partition wall could be formed. The number of manufacturing processes was greater than in Examples 1 to 3.
(Comparative Example 2)
A partition wall in which an electrode layer is formed in the partition wall in the same manner as in Comparative Example 1 except that the electrode paste is applied to a thickness of 20 μm instead of 10 μm. Produced. Although the electrode pattern could be formed on the partition wall layer, the electrode layer became thicker than Comparative Example 1, and therefore, when the partition wall paste was applied onto the laminate of the partition wall layer and the electrode pattern due to insufficient curing of the lower part of the electrode layer, The electrode pattern was peeled off, and the partition wall was cracked at the portion where the electrode was peeled off after firing.
(Comparative Example 3)
Patterning was performed in the same manner as in Example 1 except that the electrode paste 4 was used. Because the electrode paste impermeable to exposure light was used, the barrier layer under the electrode layer was insufficiently cured in the batch exposure of the barrier layer and electrode layer, and the laminate pattern of the barrier layer and electrode layer was peeled off during development, and the pattern could not be formed .
Example 4
The partition paste was applied on the base substrate using a slit die coater so that the thickness of the first partition paste layer after drying was 120 μm, and dried at 100 ° C. for 60 minutes using a hot air dryer. The electrode paste 5 was applied thereon using a slit die coater so that the thickness of the electrode paste layer after drying was 40 μm, and dried at 100 ° C. for 30 minutes using a hot air dryer. Next, the laminate was subjected to alignment exposure at an exposure amount of 100 mJ / cm ² using a 5-inch emulsion mask having a repeated pattern of dimensions shown in FIG. Thereafter, shower development was performed for 30 seconds with ultrapure water (pH: 7) to form a laminated pattern in which only the electrode layer was developed. Next, using a slit die coater, the partition paste is applied so as to cover the laminated pattern so that the thickness of the second partition paste layer after drying is 60 μm, and dried at 100 ° C. for 30 minutes using a hot air dryer. went. The laminate was subjected to alignment exposure at an exposure amount of 100 mJ / cm ² using a 5-inch emulsion mask having a repeated pattern of dimensions shown in FIG. 5, and shower-developed with a 0.2 wt% 2-aminoethanol solution for 4 minutes, A laminated pattern was formed. The laminated pattern was baked at 590 ° C., and a partition wall in which an electrode layer having a thickness of 20 μm was formed in the partition wall could be formed. Compared with Examples 1-3, the applicability | paintability to the laminated pattern of a 2nd partition paste was favorable.
(Example 5)
A plasma display was produced by the following procedure. First, the plasma display back plate was prepared by the following procedure. An address electrode pattern was formed on a “PD-200” glass substrate (13 inches) manufactured by Glass Co., Ltd. by photolithography using the electrode paste 4. Next, a dielectric layer having a thickness of 20 μm was formed on the glass substrate on which the address electrodes were formed by screen printing. Thereafter, a partition wall in which an electrode layer having a thickness of 20 μm was formed in the partition wall by the method of Example 1 was formed. Next, a phosphor layer was formed to a thickness of 20 μm by a dispenser method and fired to obtain a back plate.

Next, a 500 nm-thick MgO film was formed on a “PD200” glass substrate by an electron beam evaporation method, and a plasma display front plate was produced. The prepared front plate and back plate were sealed at 450 ° C. using a sealing frit paste containing PbO as a main component, and then xenon-neon containing 5% by volume of xenon in the space formed between the front and back substrates. A panel portion of a plasma display was manufactured by sealing a rare gas of mixed gas at a pressure of 450 mmHg. Further, a plasma display was manufactured by mounting a driver IC for driving. When the fabricated PDP was driven, an image could be displayed without any problem. The relative luminous efficiency was 160.
(Example 6)
A plasma display having an electrode thickness of 30 μm formed in the partition of the back plate was prepared in the same manner as in Example 5 except that the electrode paste 4 was applied so that the thickness of the electrode paste layer after drying was 60 μm. did. When the fabricated PDP was driven, an image could be displayed without any problem. The relative luminous efficiency was 190.
(Example 7)
A plasma display was produced in the same manner as in Example 6 except that an emulsion mask having a repeated pattern of dimensions shown in FIG. 6 was used when the first barrier rib paste layer and the electrode paste layer were collectively exposed. When the fabricated PDP was driven, an image could be displayed without any problem. The relative luminous efficiency was 215.
(Comparative Example 4)
A plasma display was produced in the same manner as in Example 5 except that the partition of the back plate was produced by the method of Comparative Example 1. When the fabricated PDP was driven, an image could be displayed without any problem. The relative luminous efficiency was 100.

  The evaluation results of Examples 1 to 7 and Comparative Examples 1 to 4 are shown in Table 2.

The flowchart which showed typically the manufacturing method of the member for displays of this invention. The perspective view which shows the 1st structural example of the member for PDP manufactured by the manufacturing method of this invention typically (partially notched drawing). The perspective view which shows the 2nd structural example of the member for PDP manufactured by the manufacturing method of this invention typically (partially notched drawing). The figure which showed the dimension of the photomask for package exposure of the 1st partition paste layer and electrode paste layer which were used in Example 1. FIG. The figure which showed the dimension of the photomask for 2nd partition paste layer partition exposure used in Example 1. FIG. The perspective view of the plasma display (with an auxiliary electrode) produced using this invention. The figure which showed the dimension of the photomask for package exposure of the 1st partition paste layer and electrode paste layer which were used in Example 7. FIG. The perspective view which shows typically the structure of the conventional alternating current (AC) type | mold plasma display.

Explanation of symbols

1: Front plate 2: Glass substrate 3: Scan electrode 4: Sustain electrode 5: Bus electrode 6: Transparent dielectric layer 7: MgO protective film 8: Back plate 9: Glass substrate 10: Address electrode 11: Dielectric layer 12: Partition 13: Red phosphor 14: Green phosphor 15: Blue phosphor 16: First partition paste layer 17: Electrode paste layer 18: First partition paste layer exposure unit 19: Electrode paste layer exposure unit 20: Photo for electrode exposure Mask 21: first barrier rib pattern 22: electrode pattern 23: second barrier rib paste layer 24: barrier rib exposure photomask 25: second barrier rib paste layer exposure part 26: laminated barrier rib pattern 27: barrier rib 30 with electrodes inside: main Partition 31: Auxiliary partition 32: Main electrode 33: Auxiliary electrode 34: Opening

Claims (2)

A photosensitive barrier rib paste composed of an inorganic component including a low softening point glass powder and an organic component including a photosensitive organic component is applied and dried to form a first barrier rib paste layer. A photosensitive organic layer is formed on the first barrier rib paste layer. A photosensitive electrode paste containing conductive particles having a component and a number average particle diameter of 1 to 200 nm is applied and dried to form an electrode paste layer, and the laminate composed of the first partition paste layer and the electrode paste layer is collectively Exposure and batch development are performed to form a first barrier rib pattern and electrode pattern laminate, and a photosensitive barrier rib paste is applied and dried to cover the first barrier pattern and electrode pattern laminate. The second barrier rib paste layer is exposed and developed to form a laminated barrier rib pattern composed of the first barrier rib pattern, the electrode pattern, and the second barrier rib pattern covering them, and the product Method for producing a display member, which comprises forming a partition wall having an electrode therein by co-firing the barrier rib pattern. An alkali-developable photosensitive barrier rib paste composed of an inorganic component including a low softening point glass powder and an organic component including a photosensitive organic component is applied and dried to form a first barrier rib paste layer, on the first barrier rib paste layer A water-developable electrode paste containing a photosensitive organic component and conductive particles having a number average particle size of 1 to 200 nm is applied and dried to form an electrode paste layer, and the first partition paste layer and the electrode paste layer The laminated body made of is collectively exposed and developed using a neutral aqueous developer to form a laminated body of the first barrier rib paste layer and the electrode pattern, and covers the laminated body of the first barrier rib paste layer and the electrode pattern. The photosensitive barrier rib paste is applied and dried to form a second barrier rib paste layer, exposed, and developed with an alkaline developer to cover the first barrier rib pattern, the electrode pattern, and the first barrier rib pattern. Forming a laminated barrier rib pattern consisting of the barrier rib pattern, the manufacturing method of the display member, which comprises forming a partition wall having an electrode therein by co-firing the laminated barrier rib pattern.

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